JPS6151069A - Anti-icing paint composition - Google Patents

Abstract

PURPOSE:To provide anti-icing paint compsn. having durable anti-icing performance, by using an organopolysiloxane resin as a base and incorporating an alkali metal compd. and a hydrophobic carboxyl group-contg. silicone compd. in the base matrix. CONSTITUTION:The titled compsn. contains 40.0-99.6wt% organopolysiloxane resin (A) of formula I [wherein R is a monovalent org. group attached to the Si atom through a C-Si bond, H; R' is H, a 1-20C alkyl, acyl, aryl, a residue of an oxime; p=1/2 (4-n-m); n and m are each less than 4 and 0<n+m<4], 0.3- 30.0wt% alkali metal compd. (B) of formula II (wherein M is an alkali metal selected from among Li, Na and K; X is an inorg. acid group, an org. acid group, hydroxyl group; a is 1-4) and 0.3-30.0wt% hydrophic silicone compd. (C) contg. at least one carboxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anti-icing coating composition, and more specifically, the present invention relates to an anti-icing coating composition, and more particularly, the composition is composed of an organoborisiloxane resin as a base, and a hydrophobic coating containing an alkali metal compound and a carboxyl group in its matrix. The present invention relates to an anti-icing coating composition which is made by uniformly dissolving or dispersing a silicon compound and is capable of preventing water from coating or strongly adhering to the surface of an object when it freezes, and which has excellent durability.

BACKGROUND OF THE INVENTION In the past, attempts have been made to reduce the icing force by applying various types of coatings to the surface of objects as one of the measures to prevent icing. As the coating material, acrylic resin-based, aluminum-based, fluororesin-based, and silicone resin-based coating materials are known. Among these, organopolysilox-gyu-san resin for each heel, which is a silicone type, is particularly widely used. For example, Soviet Patent No. 789080 discloses a two-layer silicone anti-icing coating. Also, US Patent No. 42712
No. 15 discloses an anti-icing coating using a nato-5-alco-silicone compound as an adhesion catalyst to a specific silicone resin having a carboxyl-functional group.

Although it is possible to more or less reduce icing by coating the surface of an object with these paint compositions,
K that completely prevents strong adhesion due to hydrogen bonding of ice has not yet been achieved. Therefore, the present inventor conducted basic research on the mechanism of icing, categorized it into three factors: interfacial science, physical, and thermodynamic. As a result, the inventor found that an alkaline metal compound that has a hydrogen bond dissociation effect was found. We have previously proposed a composition for an anti-icing material that exceeds the anti-icing ability of conventional coating materials, consisting of a combination of organoborishi O + sun resin and a composition made by adding a paraffin substance to the combination ( For example, Japanese Patent Application No. 136570/1983, Japanese Patent Application No. 1983-
(See Publication No. 63706).

The above-proposed composition for anti-icing material exhibits practically satisfactory anti-icing performance, but the alkali metal compound added has poor affinity with the silicone resin that is the matrix resin, and it cannot be used outdoors for long periods of time. There was a drawback that it escaped from the coating during use.

Furthermore, even when the coating film is immersed in water, there is a drawback that the active ingredient flows out slowly and the anti-icing performance gradually decreases.

Therefore, the present inventors first coated silicone oil on the coating layer 81 formed from the composition for anti-icing material to prevent the alkali metal compound from escaping from the coating. We proposed a method to improve the sustainability of the anti-icing function and at the same time further strengthen the anti-icing performance by utilizing the ability of silicone oil to reduce icing.
(See Japanese Patent Application No. 59-82640).

However, although it is possible to form a coating film with very good anti-icing performance using the method proposed above, in the actual painting process, the coating film formed from the composition for anti-icing material is Furthermore, a process of applying silicone oil is required, which goes against the current trend of streamlining and labor-saving painting processes. Therefore, in this technical field, there is a need to develop a coating composition that forms an anti-icing film that does not require a post-treatment process such as applying silicone oil, and has the same performance as when applying silicone oil. It is strongly requested.

Therefore, the inventors of the present invention have conducted intensive research to develop an anti-icing coating composition that satisfies the above-mentioned requirements, and have found that even if silicone oil is added to the anti-icing material composition proposed earlier, the objective can still be achieved. Although a coating composition could not be obtained, if a hydrophobic silicone compound containing a carboxyl group was added instead of silicone oil, a coating that could withstand long-term outdoor exposure without requiring a post-treatment step with silicone oil could be obtained. The present inventors have discovered that it is possible to obtain an anti-icing coating composition that forms a film, and have completed the present invention.

Means for Solving the Problems Thus, according to the present invention, (Shu The following average compositional unit formula % formula %) (wherein R represents a monovalent organic group bonded to silicon through a carbon-silicon bond, or hydrogen) , R' is hydrogen, C~C
2° alkyl group, acyl group, aryl group, or oxalyl group. p in the above formula is the combination (4-n-m), n and m
is a value less than 4, respectively, and the organoboryl content expressed by n + m (choose a value that satisfies the present value) is 40.0 to 99.6 parts by weight and Tn).The following formula (formula Medium M represents an alkali metal selected from Li%Na and K, X represents an inorganic acid group, hydroxyl group, or organic scattering, and a represents l-the current JI number) 0.1 An anti-icing coating composition characterized by containing 0.3 to 30.0 weight percent of a hydrophobic silicone compound having at least one carboxyl group in one molecule and (0) 0.3 to 30.0 weight percent things are provided.

Effects of the Invention The effect of the composition according to the present invention on long-term icing prevention is due to the surface properties and physical In addition to these properties, it appears as a combined effect of the effects of the alkali metal salt (DJ and the carboxyl group-containing hydrophobic silicon compound (0) described below).

That is, since the organopolysulfur resin has hydrocarbon chains arranged on its surface, its surface energy 1- is low, and since it contains extremely few polar components that tend to form hydrogen bonds, it forms a water-repellent surface.

In addition to this low energy, the icing reduction performance of the organoboric acid resin depends largely on its physical properties, especially its low-temperature properties. In other words, the rigidity of the organoborishi O + Sun resin is small, and its glass transition temperature is low, so its molecular motion is not frozen even under extremely low temperatures, for example -30°C. Not easily targeted by hydrogen bonds.

In addition, the alkali metal compound (B) and the hydrophobic silicone compound (C) containing a carboxyl group are dissolved or dispersed in the matrix resin organopolysulfur resin (A), and the silicone compound (0) is hydrophobic. It is compatible with the matrix resin and has the same effect as silicone oil without escaping outside the coating. On the other hand, the hydrophobic silicon compound (the syl group in the carboxyl group of q forms an octahedral coordination with the alkali metal of the alkali metal compound (n) (lithium and aluminum compounds are particularly easy to form), forming an anti-icing layer. At the same time, it is believed that by strongly trapping the alkali metal scrap compound in the t-m film, it exerts an excellent long-term icing prevention effect.

In the present invention, the organopolyte resin (Shu is represented by the above average compositional unit formula Rn5iCOR') mop, and can be dispersed and/or dissolved in water and an organic solvent to form a liquid state. .

R in the above formula is a monovalent organic group bonded to silicon via a carbon-silicon bond or hydrogen.

Examples of the organic group include methyl, ethyl, proyl,
Al-based groups such as silyl; cycloal-based groups such as cyclo-sil, cyclobutyl, and cyclopentyl; aryl groups such as phenyl, tolyl, silyl, and naphthyl; aral-based groups such as benzyl, phenylethyl, methylbesidyl, and naphthylpesidyl; Examples include alkenyl groups such as vinyl, allyl and oleyl; alkenyl groups such as pentadienyl and 2-cyclobutenyl; alkenylaryl groups such as vinylphenyl. Among them, lower alkyl groups having 1 to 6 carbon atoms are effective in preventing icing.

In the formula, R' is not only hydrogen but also 1 such as methyl, ethyl,
Propyl, butyl, amyl, henzyl, octyl, and other C□-C2° alkyl groups; aryl groups, C□-C8 acyl groups such as niacetyl, propionyl, butyryl; I can do it.

The above-mentioned organopolysil 0 beef sun resin used in the present invention can be used without any restriction on molecular weight as long as it can be dispersed and/or dissolved in water and organic solvents as described above. The number average molecular weight of
00 to about 1,000,000, preferably about 1,000 to about 500
The range is 000.

Furthermore, the organopolysiloxane resin having a reactive group such as a hydroxyl group or an alkoxyl group in the molecule is preferably used. Such an organopolysilomylene resin is, for example, 2-60181. ? -6188,
S, 1kyd 50, DC-3037 (Dow Cor
ning company products), KR-216, ICE-218, K
SP-IC Shin-Etsu Silicone Product), TSR-160,
TSR-165 (Tokyo Shiba M Electric product), SE 182
1%, 5EI980.5E9140.5PX211゜P
Examples include RX 305.5H237, 5H955IRTV (Toshi Shirikoshi ■ product).

The amount of the organopolysilomylene resin used is 40
．． 0-99.6% by weight, preferably 60.0-95.0
Weight range. When the amount used is more than 99.6% by weight or less than 40.0% by weight, the icing property increases significantly.

Furthermore, M in the alkali metal compound tu) represented by the general formula MaΦXe used in the present invention is Li, N
Alkali metal selected from a and K, especially Li
is suitable. In addition, X is an inorganic acid group, a hydroxyl group, or an organic acid group, and the inorganic acid group refers to the remaining portion after removing one or more hydrogen atoms that can be substituted with a metal from an inorganic acid molecule, and includes Fe, cJ3e-Drθ, and Single atoms such as IO and NO30, co3"θ, and atomic groups can be included.

In addition, the organic acid radical refers to the residue obtained by removing one or more hydrogen atoms that can be substituted with a metal from a saturated or unsaturated monocarboxylic acid or polycarboxylic acid molecule,
For example HCOOe and the general formula CH3(CH2)nC00
A sulfated monocarposi acid radical represented by O (n: an integer of 0 to 20); general formula Malay: / unsaturated 0 such as acid, oleic acid, linoleic acid, etc.
8; -to other a stone ase ooc-(cyon>2
Polyvalent carposi acid radicals such as -cooe; and the like.

Further, a is determined depending on the type of the non-ia acid radical or the organic acid radical, and is usually an integer of 1 to 4.

Therefore, the following can be exemplified as representative examples of the alkali metal compounds represented by the above formula.

LsF %Ls(:13, LiBr s Lil %N
aF s NaCl; 3, NaBr % Mal s'
KF' sKα1KEr, Kl s'LxNO3,
NaNO3, KNO3, Li2Co, , Na2CO3
,K2No,,Ls 3/'O(,,Na3/'OI4
, KPOJ4, Li25OI4, Na2SO4, K2
S0. LiMnO4, A/aMnO4s KMnQa
sLi2Cr20. ,,/Va2Cr207,K2Cr
2O7, Li, 5inasL s 2SiO3, Noa
Sinas Na2SiO3, K4SiOI4, K2S
t O3, L 1BO2, NaSO3, KBO2, L
t3VQI4, Na3FO(h,K,VO,,L
s 2WOa, 7Va2TFOa, K2WOa; HCO
OLi%HCOONn, HCOOK, Li2
C20,, Na2C2014, K2C2O4, CH3C
OOLi, CH3COONa.

CH3CH3K% C2H3COOLt -LsOOC
-CH2-COOLt - Lithium citrate, sodium citrate, potassium citrate, lithium tartrate, lithium trimellitate, lithium pyromellitate, etc. These alkali metal compounds can be used alone or in combination of two or more, and the blending amount is from 0.1 to 30.0 cm, preferably from 0.5 to 1000" (depending on the amount).

When the amount of the alkali metal compound is less than 0.1% by weight, the anti-icing effect is significantly reduced, and when it exceeds 30.0% by weight, the physical properties of the coating film are deteriorated.

Among these alkali metal compounds, chloride has the greatest anti-icing effect. However, when such strong acid salts are used, they have the property of causing rust on metal materials, so care must be taken when using them. Next, carbonates, silicates and acetates have the greatest anti-icing effect, and these are preferable because they have a long-lasting anti-icing effect and are less likely to cause rust. Furthermore, among these alkali metal compounds, lithium compounds are preferred because they have a greater anti-icing effect than other sodium compounds and potassium compounds.

The carboxylic group-containing hydrophobic silicone compound (0) used in the present invention is a hydrophobic silicone compound having at least one carboxylic group in the molecule, and preferably has a molecular weight of about 100 to about 50,000. Approximately 130~
A range of approximately 10,000 is used. Further, the amount of the introduced carboxyl group is about 0. O ranges from 1 to about 50% by weight, preferably from about 0.1 to about 35% by weight, and more preferably from about 1 to about 10% by weight. If the content of carboxylic groups is less than 0.01 weight meters, the alkali metal compound (13) dissolved and dispersed in the matrix resin cannot be sufficiently captured and long-term anti-icing properties cannot be obtained. . On the other hand, if the content of sil groups in the carboxyl group exceeds 50% by weight, the silicone compound (C1 itself is highly hydrophilic) has a low affinity with the matrix resin, resulting in poor coating film performance. At the same time, icing properties increase.

That is, the hydrophobicity of the silicon compound (0) used in the present invention means that the content of carboxylic groups in the silicon compound is in the range of about 50% by weight or less, and the silicon compound is resistant to water at room temperature. It means to exhibit the property of being immiscible.

The above-described hydrophobic silicosyl group-containing compound (0
) As representative examples, the following can be exemplified.

CH3CN.

CH,CH3 CH3CH.

CH3'11'0OC-CH-8i-CH2-COOHi13 CH3 H3 CH3cIi3 In addition to the above, carboxy-modified silicone oil in which a carboxyl group is introduced into the side chain of silicone oil can be mentioned. The amount of carboxyl groups introduced into the carboxy-modified silicone oil is usually about 0.1 to about 5 fj, preferably about 0.3 to about 2 fj! , within the range of 俤. Examples of the carboxy-modified silicone oil include 5F-s+I8 (Toshi Silicone ■ product).

The above-mentioned carbo+syl group-containing hydrophobic silicon compound (0
) may be used alone or in combination of 2fi4 or more. be able to. Its blending amount is 0.3~
30.0% by weight, preferably 1.0-10. I am in charge of ON amount. If the blending amount of the component (C) is less than 0.3 weight gc, long-term icing prevention properties during outdoor exposure will not be obtained;
If it exceeds 0.0% by weight, the physical properties and weather resistance of the coating film will deteriorate.

The anti-icing coating composition of the present invention includes the above-mentioned (A) and (I).
Components I) and (0) are essential components, and if desired, paraffinic substances may be added to improve the sustainability of the anti-icing ability and to improve ice-r! The shear breaking force at the L membrane interface can be reduced. The action of the paraffin substance is an orientation effect on the surface, in which non-polar hydrocarbon chains are arranged on the surface, lowering the surface energy and at the same time imparting lubricity to the surface. The paraffin substances used are conventionally known liquid paraffin and solid paraffin, and the former liquid paraffin mainly consists of hydrocarbons having 10 to 24 carbon atoms and has an average molecular weight of about 150 to 24.
It is liquid at room temperature of 250℃, and is usually mixed with white oil (
It is also called white oil. On the other hand, the latter solid paraffin is mainly composed of hydrocarbons having about 18 to 30 carbon atoms, has an average molecular weight of about 250 to 350, and has a melting point of 50.
It is a substance that can be dissolved or dispersed in a solid ordinary organic solvent at room temperature below .degree. C., preferably below 40.degree.

In the present invention, liquid paraffin is used, especially the pour point (P
Liquid paraffin having a low temperature of −5° C. or lower is preferred because it maintains fluidity even at temperatures below the freezing point and is extremely effective in reducing shear fracture force.

As a representative example of paraffin, for example, as liquid paraffin, the product name 'Carnation 's' I
CIoarol"1"Blandor',' 13g
nol', Kaydol, etc. (all from U.S. Witco
On the other hand, solid paraffin includes paraffin wax 110 manufactured by Nippon Seiro Co., Ltd.
．． 115.120, etc.

Further, when a paraffin substance is blended into the composition of the present invention, the amount is 0.2 to 4 OTfL, preferably 0.5 ~
It is in the range of 20% by weight. If the content of the paraffin substance is less than 0.2 parts by weight, no reduction in the shear breaking force at the ice-coating film interface is observed, while if it exceeds 40 parts by weight, the physical properties and durability of the coating film will deteriorate.

In addition, the composition of one 'A''A contains, as necessary, known pigments, extender pigments, or dyes that are commonly used in paints. It can be added within a range of 120ffiQ1 or less.Other surfactants and additives can also be added as appropriate.

The anti-icing coating composition of the present invention is prepared as described above (mu).
This is done by mixing the components, (B) component, (01 component), and other components as necessary.The method of mixing is performed using a steel ball mill, a pebble mill, an attritor, etc., which are general dispersion methods. When preparing the composition for paint, an organic solvent is used as appropriate.The solvent may be any solvent as long as it can dissolve the base resin, organoborishi Ogyosan resin. Solvents commonly used in paints, such as hydrocarbons, ketone groups, esters, and alcohols, can be used.If the paint is an aqueous dispersion type, water is naturally used.

In addition to being applied as a top coat on top of a paint film, the composition can also be applied directly to metals, plastics, glass, wood materials, and the like. The composition can also be used as a molded article by laminating it on the surface of an object.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Parts and parts indicate heavy active parts and weight % unless otherwise specified.

Example 1 Addition-polymerized organopolysiloxane resin (trade name: Toshi Silikoshi SE-1821, non-volatile content 4(1) 85 parts, 5 parts of lithium acetate, 10 parts of trimethylsilyl butyric acid with a diameter of 3 mm of Alni silicate nappies) Red
Added to Devil type paint conditioner and allowed to disperse for 30 minutes. Then, SE-1 was added to this as a curing agent.
821Cat (manufactured by Toshi Silicone Co., Ltd., platinum-based catalyst) 1
The composition obtained by adding 0 parts was applied onto a stainless steel plate for icing test using an applicator and phosphorized at 100°C for 5 minutes. The dry film thickness at this time was 45 μm. The thus obtained painted board was fixed at an angle of 45° facing south (painted board I) and exposed outdoors for 06 months (1M!).
Plate 2) and one immersed in water at room temperature for 240 hours (Coated Plate 3)
) was frozen at 10° C. for 2 hours and its icing shear fracture strength was measured using the test method described below.

Example 2 90 parts of addition-polymerized organopolysiloxane resin (trade name: Nitoshi Silicone 5EX-211, non-volatile content: 40%, number average molecular weight of about 300,000 or more), 2 parts of lithium metasilicate, trimethylsilyl acetic acid, and Carnation ( 10 parts of liquid paraffin (product name: Wilco Chttmica 1, USA, pour point -7°C) was dispersed in the same manner as in Example 1. Next, platinum-based catalyst 5RX-2 was added to this material.
A composition obtained by adding 0.6 part of 12Cat (Toshi Shirikoshi Co., Ltd. iA) was coated in the same manner as in Example 1, and heated at 150°C.
Heating was carried out for minutes to obtain a 20 μm dry membrane. The obtained coated plate was treated in the same manner as in Example 1, and the icing shear fracture strength was measured when it was frozen at -10°C for 2 hours using the test method described below.

Example 3 Condensation polymerization type organoborisu 0 medium resin (trade name: Nitoshi Silicone: JSE-9140, non-volatile content 40%) 80
1 part, 35 parts of sodium trimethylsilylbutyrate silicate, and 20 parts of the fluidized buffine used in Example 2 were dispersed and coated in the same manner as in Example 1, and dried at room temperature for 48 hours. The dry coating film at this time was 7 μm. The obtained coated plate was treated in the same manner as in Example 1, and the icing shear fracture strength was measured when it was frozen at -10°C for 2 hours using the test method described below.

Example Now example! A coated plate was prepared and tested in the same manner as in Example 1, except that 30 parts of trimethylsilylbutyric acid and 70 parts of organopolysil O + resin were used.

Example 5 Example! In place of lithium acetate, 3 parts of lithium citrate was used instead of trimethylsilylacetic acid. CH3 Li0OC-CH2-C112-S i -CH2-C
H2-C0OHCH.

A coated plate 1c was prepared in the same manner as in Example 1, except that 7.5 parts of the resin and 92.5 parts of the organopolysil beef sun resin were used and subjected to the test.

Example 6 In Example 2, 5 parts of potassium carbonate was used instead of lithium metasilicate, and carboxylic modified silicone oil (trade name: 5F-8418 was used instead of trimethylsilyl acetate).
, made by Toshi Silicone:/@, molecular weight approximately 30,000, C0O
A coated plate was prepared and tested in the same manner as in Example 2, except that 15 parts of H content (approx. 1.2%) and 80 parts of organopolysilosashi resin were used.

Icing shear fracture strength test method: A coating film (2
Place the stainless steel link (3) (inner area 5d) on top of ), place this in a freezing test constant temperature bath at -1 part ℃, and
Pre-cool for 0 minutes. Next, distilled deionized water 2R1 maintained at 5° C. is poured into the link (3) and frozen, thereby obtaining ice (4) that adheres to the surface of the subject. -1
After being left in this state for 2 hours at 10°C, a metal moving rod (
Hit the ring (3) with the axis) (6) and make the ice (4
) was measured (unit: Kv/
cJ).

[Brief explanation of the drawing]

FIG. 1 is a sectional view of an apparatus for testing the icing properties of the composition for anti-icing materials of the present invention. (S)・・・Stainless steel plate, (2)・・・・・・
Paint film, (3)...Stainless steel link, (4)...
... Ice, (5) ... Actuation rod (and more) Figure 1

Claims (1)

[Claims] (1) (A) The following average compositional unit formula RnSi(OR')mOp (wherein R represents a monovalent organic group bonded to silicon through a carbon-silicon bond or hydrogen, and R' is Hydrogen, C_1~
Indicates an alkyl group, acyl group, aryl group, or oxime residue of C_2_0. p in the above formula is 1/2 (4-nm)
, n and m each have a value less than 4, and 0<n+m<
This value satisfies 4. 40.0 to 99.6 parts by weight of an organopolysiloxane resin represented by 0.1 to 30.0% by weight of an alkali metal compound (representing an acid radical, hydroxyl group or organic acid radical, a represents an integer of 1 to 4) and (C) having at least one carboxyl group in one molecule An anti-icing coating composition containing 0.3 to 30.0% by weight of a hydrophobic silicone compound.